JP2004204191A - Non-transferring water repellent film - Google Patents
Non-transferring water repellent film Download PDFInfo
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- JP2004204191A JP2004204191A JP2002378153A JP2002378153A JP2004204191A JP 2004204191 A JP2004204191 A JP 2004204191A JP 2002378153 A JP2002378153 A JP 2002378153A JP 2002378153 A JP2002378153 A JP 2002378153A JP 2004204191 A JP2004204191 A JP 2004204191A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
- C03C17/009—Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/30—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Abstract
Description
【0001】
【発明の属する技術分野】
本発明は、基材表面に形成した不転写性を呈する撥水膜に関し、更に詳しく述べると、撥水膜用液組成物を基材表面に塗布し、乾燥することで形成される撥水膜において、ハンドリング治具を介して撥水成分の転写が起こらないようにした不転写性撥水膜に関するものである。
【0002】
【従来の技術】
【特許文献1】
特開2001−172417公報
【特許文献2】
特表2002−529355公報
【0003】
ガラス板その他の基材に撥水性を付与するために、基材表面に撥水膜を形成することがある。このような撥水膜は、例えばシリコンアルコキシドまたはその加水分解物、フルオロアルキル基含有シラン化合物、及び酸を溶媒に溶解した撥水膜用液組成物を基材表面に塗布し、乾燥することで形成される(例えば特許文献1参照)。特に、自動車用の窓ガラスでは、このような撥水処理が行われることも多い。
【0004】
ところで、自動車の製造工程では、種々の車種又は仕様の自動車が製造されるが、それに伴い、撥水膜を形成した窓ガラス板と通常の(撥水膜を有しない)窓ガラス板とが混在してラインに供給される。
【0005】
これらの窓ガラス板は、吸盤構造のハンドリング治具で取り扱われるが、その際、ハンドリング治具を撥水膜に対して吸着させるため、該ハンドリング治具の表面に撥水成分が付着することがある。次に、このハンドリング治具を用いて通常の窓ガラス板を取り扱うと、該ハンドリング治具に付着していた撥水成分が通常の(撥水膜を有しない)窓ガラス板に転写(再付着)してしまう。このような転写現象は、撥水膜の品質を低下させるばかりでなく、転写した不要な撥水成分の除去に手間がかかるなど様々な不具合を招来する。
【0006】
そこで、このような問題を解決するための対策として、撥水膜の表面に転写防止用の粘着フィルムを貼付する方法、撥水性能に悪影響を与えず水で洗い流せる界面活性剤を撥水膜の上に薄膜状に塗布する方法(特許文献2参照)などが行われてきた。
【0007】
【発明が解決しようとする課題】
しかし転写防止用の粘着フィルムを貼付する方法は、フィルム貼付作業、ハンドリング後のフィルム剥離作業など、作業工数が増加するし、使用したフィルムの廃棄処分も必要となる。特に昨今の環境対策から、廃棄物量の増大は問題である。
【0008】
また界面活性剤を塗布する方法は、塗布工数の増加、除去工程(水シャワー)の設置、界面活性剤が混入した廃水の処理などが必要となる。
【0009】
本発明の目的は、撥水膜自体に転写が起こらないような性質を付与することにより、フィルム貼着や界面活性剤の塗布などの作業を不要として、工数増加や環境負荷の増大が生じないようにした不転写性撥水膜を提供することである。
【0010】
【課題を解決するための手段】
本発明者らは、かねてより撥水膜の研究開発を行っており、表面の平滑性を高めることにより水滴の転がり性を高め、また基板との結合力を高めることにより高い耐擦傷性、耐候性を有する撥水膜を開発した。それが、シリコンアルコキシドまたはその加水分解物、フルオロアルキル基含有シラン化合物、及び酸を溶媒に溶解した撥水膜用液組成物を基材表面に塗布し、乾燥することで形成される撥水膜である。更に、この技術開発を進めていく過程で、特定の組成範囲に限定すると、撥水性を呈することは無論のこと、その他に、不転写性(転写が起こらない性質)が新たに発現することを見出した。本発明は、かかる現象の知得に基づきなされたものである。
【0011】
本発明は、シリコンアルコキシド、フルオロアルキル基含有シラン化合物、及び酸を溶媒に溶解した撥水膜用液組成物を基材表面に塗布し、乾燥することで形成される撥水膜において、
撥水膜用液組成物として、
(A)シリコンアルコキシドまたはその加水分解物:0.05〜0.20質量%(シリカ換算)
(B)フルオロアルキル基含有シラン化合物:0.001〜0.003質量%(シリカ換算)
(C)酸:(0.01〜0.30)/酸の価数mol/l
(D)水:0.5〜2.0質量%
(E)アルコール系溶媒:残部
からなる組成範囲内の液組成物を用いて形成され、膜に接触するハンドリング治具を介して撥水成分の転写が起こらないようにしたことを特徴とする不転写性撥水膜である。
【0012】
本発明において、撥水膜の表面におけるフッ素濃度は、フッ素原子とケイ素原子との比で0.8〜1.2とするのが好ましい。(A)シリコンアルコキシドまたはその加水分解物に対する(B)フルオロアルキル基含有シラン化合物の比が小さすぎると撥水膜の撥水性能が低下し、逆に大きすぎると撥水膜の機械的耐久性が低下する。従って、破水膜としてのフッ素原子とケイ素原子の比としては、上記の範囲が好ましいのである。
【0013】
また本発明は、このような撥水膜で被覆されている物品である。種々の物品が可能であるが、なかでも典型的な物品は、自動車用の窓ガラス板である。前記の撥水膜用液組成物をガラス板表面に塗布し、乾燥することで形成される。
【0014】
【発明の実施の形態】
本発明に係る撥水膜は、
(A)シリコンアルコキシドまたはその加水分解物:0.05〜0.20質量%(シリカ換算)
(B)フルオロアルキル基含有シラン化合物:0.001〜0.003質量%(シリカ換算)
(C)酸:(0.01〜0.30)/酸の価数mol/l
(D)水:0.5〜2.0質量%
(E)アルコール系溶媒:残部
からなる組成範囲内の撥水膜用液組成物を用る。そして、この撥水膜用液組成物を基材表面に塗布し、乾燥することで撥水膜が形成する。得られた撥水膜は不転写性を呈し、それに吸盤構造のハンドリング治具を吸着させ、更に他の通常のガラス板を吸着させても、撥水成分の転写は起こらない。
【0015】
従来技術においてハンドリングの際に撥水成分の転写(再付着)が生じていた理由は、余剰の撥水成分が存在していたためと考えられる。つまり、ガラス表面もしくは下地部分の化学結合サイト数に対して、撥水性能を示すフルオロアルキル基含有シラン化合物の数が余剰に存在するため、余剰分は化学結合せず、表面上に弱い物理吸着(ファンデルワールス力により付着)しているのみであると推測される。そのため、吸盤などのハンドリング治具により撥水膜の表面に強い力が加わると、余剰撥水成分が容易にハンドリング治具に付着し、それが他の物品を取り扱う時に転写(再付着)するのである。しかし本発明では、基材表面の化学結合サイト数に対して、撥水性能を呈するフルオロアルキル基含有シラン化合物の数を最適にしたことにより、表面上に存在する撥水成分は全て化学結合によって存在させており、余剰撥水成分が存在しないために転写が起こらないのである。
【0016】
そのため具体的には前記のように、シリコンアルコキシドまたはその加水分解物は、シリカ換算で0.05〜0.20質量%の範囲内とする。その範囲よりも添加量を多くした場合には、反応サイト数を増やすことはできるが、同時に膜厚も厚くなることから、機械的耐久性が低下する不具合が生じる。逆に、添加量を少なくした場合、膜厚が薄くなることから、機械的強度を確保することができるが、反応サイト数を減らすことになるために、撥水性能自体が低下する不具合が生じる。
【0017】
フルオロアルキル基含有シラン化合物は、シリカ換算で0.001〜0.003質量%とする。その範囲よりも添加量を多くした場合、撥水成分が増えることから撥水性能は高まると考えられるが、多すぎた場合には、限られた反応サイト数以上に存在する撥水成分は、余剰分として基材に化学結合することなく弱い分子間力により吸着しただけとなり、転写が起こる。添加量を少なくした場合、撥水成分の絶対量が少なくなることから撥水性能は低下する。
【0018】
酸の濃度は、シリコンアルコキシドまたはその加水分解物とフルオロアルキル基含有シラン化合物との組成比ファクタによって決定される。酸濃度が高くなると液中のシリコンアルコキシドまたはその加水分解物の縮合反応が起こり易くなり、溶液のポットライフが短くなる。酸濃度が低くなると、液中のシリコンアルコキシドまたはその加水分解物の縮合反応が起こり難くなり、膜の耐久性、機械的強度を十分に保つことができない。
【0019】
水の濃度も、シリコンアルコキシドまたはその加水分解物とフルオロアルキル基含有シラン化合物との組成比ファクタによって決定される。水の濃度が低いほど、縮合反応が起こり易くなる。水の濃度が高くなると、溶液中のシリコンアルコキシドまたはその加水分解物の加水分解反応が促進され、かつ脱水縮合反応が起こり易くなるため、溶液のポットライフが短くなり、また溶液の塗布後の乾燥の際に膜厚のむらが生じるなどの不具合が生じる。
【0020】
撥水膜用液組成物の基材表面への塗布は、公知の任意の方法を用いてよい。乾燥は室温で行ってよく、勿論、加熱(150℃程度以下の温度で)乾燥してもよい。乾燥後、撥水膜の緻密性を更に高めるために、300℃程度以下の温度で焼成することも可能である。
【0021】
【実施例】
次に、シリコンアルコキシドまたはその加水分解物、フルオロアルキル基含有シラン化合物、及び酸(塩酸)を溶媒に溶解した撥水膜用液組成物について、本発明で規定する範囲に含まれる撥水膜用液組成(実施例1−3)と範囲外の撥水膜用液組成(比較例1−4)のコーティング液を調製し、ガラス板の表面に塗布し乾燥して撥水膜を形成した。各実施例及び各比較例の液組成と不転写性評価の結果を表1に示す。なお、括弧内はハンドリング回数を示す。
【0022】
【表1】
【0023】
不転写性評価(転写の有無の評価)は、次のようにして行った。
1.サンプル(表面に撥水膜を形成したガラス板、質量:約4kg)の撥水面に対してハンドリング治具である吸盤(吸盤材質:フッ素ゴム、吸盤径:80mmφ)を圧接して吸着させる(吸着圧:−85kPa)。
2.吸着させた後、サンプルを30秒間垂直保持し、吸盤面に負荷をかける。この時、同一箇所では吸着させずに、常に新しい撥水面に吸盤を吸着させ、負荷をかける。
3.任意回数毎に洗浄(セリコ洗浄)した非撥水ガラス面に同条件で吸盤を吸着させる。非撥水ガラスも同一箇所には吸着させない。
4.非撥水ガラス面を水で濡らし、吸盤跡で水を弾くか否かを確認する。
5.XPS(X線光電子分光分析)によって非撥水ガラス面の表面撥水成分の定量を行い、転写の有無を確認する。
6.吸盤状に水を弾かない場合、または表面撥水成分が検出されない場合を転写無しと判断し、吸盤状に水を弾いた場合、または表面撥水成分が検出された場合を転写有りと判断する。
【0024】
本発明に係る実施例1−3は、いずれも1000回のハンドリングに対しても転写は生じなかった。それに対して、シリコンアルコキシドまたはその加水分解物の少ない比較例1は、1回のハンドリングで弱い転写が起こり、10回のハンドリングで転写があった。またシリコンアルコキシドまたはその加水分解物が少なく且つフルオロアルキル基含有シラン化合物が多い比較例2と比較例4は、共に1回のハンドリングでも転写が生じた。更にシリコンアルコキシドまたはその加水分解物が多く且つフルオロアルキル基含有シラン化合物も多い比較例3は、1回のハンドリングで弱い転写があり、10回のハンドリングで転写があった。
【0025】
このように、本発明で規定する範囲に含まれる撥水膜用液組成を用いた撥水膜は、範囲外の撥水膜と比較して、不転写性という点で、明確な質的相違が認められた。
【0026】
更に参考例として、他の構成の撥水膜についても転写の有無を調査した。
参考例1:クロロシラン+アルコール溶媒でシリカ下地膜を形成し、次にFAS-C1撥水成分の塗り込みによる成膜(2層式)
参考例2:ジメチルシロキサン撥水成分を酸のもとでの塗り込みによる成膜
これらの2種では、いずれも10回以内のハンドリングで転写が起こった。
【0027】
【発明の効果】
本発明は上記のように、シリコンアルコキシドまたはその加水分解物、フルオロアルキル基含有シラン化合物、及び酸を溶媒に溶解した撥水膜用液組成物を特定の組成範囲に限定したことにより、撥水膜自体に不転写性(転写が起こらないという性質)が発現するため、フィルムを貼着したり界面活性剤を塗布する等の転写防止対策が不必要となる。その結果、工数や設備の増加が生じず、環境負荷の増加も生じないなどの効果が得られる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a non-transferable water-repellent film formed on a substrate surface, and more specifically, a water-repellent film formed by applying a liquid composition for a water-repellent film to a substrate surface and drying. The present invention relates to a non-transferable water-repellent film which prevents transfer of a water-repellent component via a handling jig.
[0002]
[Prior art]
[Patent Document 1]
JP 2001-172417 A [Patent Document 2]
JP 2002-529355 A
In order to impart water repellency to a glass plate or other substrate, a water repellent film may be formed on the surface of the substrate. Such a water-repellent film is formed, for example, by applying a silicon alkoxide or a hydrolyzate thereof, a fluoroalkyl group-containing silane compound, and a liquid composition for a water-repellent film obtained by dissolving an acid in a solvent to a substrate surface and drying. (See, for example, Patent Document 1). In particular, such water-repellent treatment is often performed on window glasses for automobiles.
[0004]
By the way, in an automobile manufacturing process, automobiles of various types or specifications are manufactured, and accordingly, a window glass plate having a water-repellent film and a normal (no water-repellent film) window glass plate coexist. And supplied to the line.
[0005]
These window glass plates are handled by a suction jig handling jig. At this time, a water repellent component may adhere to the surface of the handling jig because the handling jig is adsorbed to the water repellent film. is there. Next, when a normal window glass plate is handled using this handling jig, the water-repellent component adhering to the handling jig is transferred (re-attached) to a normal (no water-repellent film) window glass plate. )Resulting in. Such a transfer phenomenon not only reduces the quality of the water-repellent film, but also causes various troubles such as troublesome removal of the transferred unnecessary water-repellent component.
[0006]
Therefore, as a measure to solve such a problem, a method of attaching an adhesive film for preventing transfer to the surface of the water-repellent film, a surfactant that can be washed away with water without adversely affecting the water-repellent performance of the water-repellent film is used. A method of applying a thin film thereon has been performed (see Patent Document 2).
[0007]
[Problems to be solved by the invention]
However, the method of sticking an adhesive film for preventing transfer increases the number of work steps such as film sticking work and film peeling work after handling, and also necessitates disposal of the used film. Particularly, due to recent environmental measures, an increase in the amount of waste is a problem.
[0008]
In addition, the method of applying a surfactant requires an increase in the number of coating steps, installation of a removal step (water shower), treatment of wastewater mixed with a surfactant, and the like.
[0009]
An object of the present invention is to provide a property such that transfer does not occur to the water-repellent film itself, so that operations such as film sticking and application of a surfactant are unnecessary, and an increase in man-hours and environmental load does not occur. An object of the present invention is to provide a non-transferable water repellent film as described above.
[0010]
[Means for Solving the Problems]
The present inventors have been conducting research and development of a water-repellent film for some time, and have enhanced the smoothness of the surface to enhance the rolling properties of water droplets, and also increased the bonding force with the substrate to achieve high scratch resistance and weather resistance. We have developed a water-repellent film that has good properties. A water-repellent film formed by applying a liquid composition for a water-repellent film in which a silicon alkoxide or a hydrolyzate thereof, a fluoroalkyl group-containing silane compound, and an acid are dissolved in a solvent to a substrate surface and drying the composition. It is. Furthermore, during the course of this technological development, it is obvious that if the composition is limited to a specific composition range, it will not only exhibit water repellency, but also exhibit a new non-transfer property (the property that does not cause transfer). I found it. The present invention has been made based on the knowledge of such a phenomenon.
[0011]
The present invention provides a water-repellent film formed by applying a liquid composition for a water-repellent film in which a silicon alkoxide, a fluoroalkyl group-containing silane compound, and an acid are dissolved in a solvent to a substrate, and drying the composition.
As a liquid composition for a water-repellent film,
(A) Silicon alkoxide or hydrolyzate thereof: 0.05 to 0.20% by mass (in terms of silica)
(B) Fluoroalkyl group-containing silane compound: 0.001 to 0.003% by mass (in terms of silica)
(C) Acid: (0.01 to 0.30) / valency of acid mol / l
(D) Water: 0.5 to 2.0% by mass
(E) Alcohol-based solvent: formed using a liquid composition within the composition range consisting of the remainder, and preventing transfer of a water-repellent component via a handling jig in contact with the film. It is a transferable water repellent film.
[0012]
In the present invention, the fluorine concentration on the surface of the water-repellent film is preferably 0.8 to 1.2 in terms of the ratio of fluorine atoms to silicon atoms. If the ratio of (B) the fluoroalkyl group-containing silane compound to (A) silicon alkoxide or its hydrolyzate is too small, the water-repellent performance of the water-repellent film is reduced. Decreases. Therefore, the above range is preferable as the ratio between the fluorine atom and the silicon atom as the water breakage film.
[0013]
Further, the present invention is an article covered with such a water-repellent film. A variety of articles are possible, but a typical article is an automotive glazing. It is formed by applying the liquid composition for a water-repellent film to the surface of a glass plate and drying.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The water-repellent film according to the present invention,
(A) Silicon alkoxide or hydrolyzate thereof: 0.05 to 0.20% by mass (in terms of silica)
(B) Fluoroalkyl group-containing silane compound: 0.001 to 0.003% by mass (in terms of silica)
(C) Acid: (0.01 to 0.30) / valency of acid mol / l
(D) Water: 0.5 to 2.0% by mass
(E) Alcohol-based solvent: A liquid composition for a water-repellent film having a composition range of the remainder is used. Then, the liquid composition for a water-repellent film is applied to the surface of a substrate and dried to form a water-repellent film. The obtained water-repellent film exhibits non-transfer properties, and the transfer of the water-repellent component does not occur even if a handling jig having a suction cup structure is adsorbed on the film and another ordinary glass plate is adsorbed thereon.
[0015]
The reason why the transfer (reattachment) of the water-repellent component occurred during handling in the prior art is considered to be the existence of an excess water-repellent component. In other words, since the number of fluoroalkyl group-containing silane compounds exhibiting water repellency exists in excess of the number of chemical bonding sites on the glass surface or the underlying portion, the excess is not chemically bonded and weak physical adsorption on the surface It is presumed that they are only adhered (attached by Van der Waals force). Therefore, if a strong force is applied to the surface of the water-repellent film by a handling jig such as a suction cup, the surplus water-repellent component easily adheres to the handling jig and is transferred (re-attached) when handling other articles. is there. However, in the present invention, by optimizing the number of fluoroalkyl group-containing silane compounds exhibiting water repellency with respect to the number of chemical bonding sites on the substrate surface, all the water repellent components present on the surface are chemically bonded. That is, transfer does not occur because there is no excess water repellent component.
[0016]
Therefore, specifically, as described above, silicon alkoxide or its hydrolyzate is in the range of 0.05 to 0.20 mass% in terms of silica. When the addition amount is larger than the above range, the number of reaction sites can be increased, but at the same time, the film thickness is also increased, which causes a problem that the mechanical durability is reduced. Conversely, when the addition amount is reduced, since the film thickness is reduced, mechanical strength can be secured, but since the number of reaction sites is reduced, a problem that the water repellency performance itself is reduced occurs. .
[0017]
The fluoroalkyl group-containing silane compound is 0.001 to 0.003% by mass in terms of silica. If the addition amount is larger than that range, the water-repellent component is thought to increase because the water-repellent component increases, but if too large, the water-repellent component present in a limited number of reaction sites or more is As a surplus, it is merely adsorbed by a weak intermolecular force without chemically bonding to the substrate, and transfer occurs. When the amount of addition is reduced, the water repellency is reduced because the absolute amount of the water repellent component is reduced.
[0018]
The concentration of the acid is determined by a composition ratio factor between the silicon alkoxide or its hydrolyzate and the fluoroalkyl group-containing silane compound. When the acid concentration is high, a condensation reaction of silicon alkoxide or a hydrolyzate thereof in the liquid is likely to occur, and the pot life of the solution is shortened. When the acid concentration is low, the condensation reaction of the silicon alkoxide or the hydrolyzate thereof in the liquid is difficult to occur, and the durability and mechanical strength of the film cannot be sufficiently maintained.
[0019]
The concentration of water is also determined by the composition ratio factor between the silicon alkoxide or its hydrolyzate and the fluoroalkyl group-containing silane compound. The lower the concentration of water, the easier the condensation reaction will take place. When the concentration of water is high, the hydrolysis reaction of silicon alkoxide or its hydrolyzate in the solution is accelerated, and the dehydration condensation reaction is easily caused, so that the pot life of the solution is shortened, and drying after application of the solution is performed. In such a case, problems such as unevenness of the film thickness occur.
[0020]
The coating of the liquid composition for a water-repellent film on the surface of a substrate may be performed by any known method. Drying may be performed at room temperature, and of course, may be performed by heating (at a temperature of about 150 ° C. or lower). After drying, in order to further increase the density of the water-repellent film, baking can be performed at a temperature of about 300 ° C. or less.
[0021]
【Example】
Next, a liquid composition for a water-repellent film in which a silicon alkoxide or a hydrolyzate thereof, a fluoroalkyl group-containing silane compound, and an acid (hydrochloric acid) are dissolved in a solvent is used for a water-repellent film included in the range specified in the present invention. A coating liquid having a liquid composition (Example 1-3) and a liquid composition for a water-repellent film out of the range (Comparative Example 1-4) was prepared, applied to the surface of a glass plate, and dried to form a water-repellent film. Table 1 shows the liquid compositions and the results of the evaluation of the non-transferability of each of the examples and comparative examples. The number in parentheses indicates the number of times of handling.
[0022]
[Table 1]
[0023]
The non-transferability evaluation (evaluation of the presence or absence of transfer) was performed as follows.
1. A suction jig (suction material: fluorine rubber, suction diameter: 80 mmφ), which is a handling jig, is pressed against the water-repellent surface of a sample (a glass plate having a water-repellent film formed on its surface, mass: about 4 kg) to adsorb it (adsorption) Pressure: -85 kPa).
2. After the adsorption, the sample is held vertically for 30 seconds and a load is applied to the suction cup surface. At this time, a suction cup is always adsorbed to a new water-repellent surface without being adsorbed at the same location, and a load is applied.
3. A suction cup is adsorbed to the non-water-repellent glass surface that has been washed (cerico-washed) at an arbitrary number of times under the same conditions. Non-water-repellent glass is not adsorbed at the same location.
4. Wet the non-water-repellent glass surface with water and check if the water is repelled by the suction cup mark.
5. The surface water-repellent component on the non-water-repellent glass surface is quantified by XPS (X-ray photoelectron spectroscopy) to confirm the presence or absence of transfer.
6. When no water is repelled in a sucker shape or when no surface water-repellent component is detected, it is determined that there is no transfer. When water is repelled in a sucker shape or when a surface water-repellent component is detected, it is determined that there is a transfer. .
[0024]
In Examples 1-3 according to the present invention, no transfer occurred even after 1000 times of handling. On the other hand, in Comparative Example 1 in which the amount of silicon alkoxide or its hydrolyzate was small, weak transfer occurred in one handling and transfer occurred in 10 handlings. In Comparative Example 2 and Comparative Example 4 in which the amount of silicon alkoxide or hydrolyzate thereof was small and the amount of the fluoroalkyl group-containing silane compound was large, transfer occurred even in a single handling. Further, Comparative Example 3 in which a large amount of silicon alkoxide or a hydrolyzate thereof and a large amount of a silane compound containing a fluoroalkyl group were used, a weak transfer was obtained by one handling, and a transfer was performed by 10 handlings.
[0025]
As described above, the water-repellent film using the liquid-repellent film liquid composition included in the range specified in the present invention has a clear qualitative difference in terms of non-transferability as compared with the water-repellent film outside the range. Was observed.
[0026]
Further, as a reference example, the presence / absence of transfer was investigated for a water-repellent film having another configuration.
Reference Example 1: A silica base film is formed with a chlorosilane + alcohol solvent, and then a film is formed by applying a FAS-C1 water-repellent component (two-layer type).
Reference Example 2: Film formation by applying a dimethylsiloxane water-repellent component under an acid In both cases, transfer occurred within 10 times of handling.
[0027]
【The invention's effect】
As described above, the present invention limits the liquid composition for a water-repellent film in which a silicon alkoxide or a hydrolyzate thereof, a fluoroalkyl group-containing silane compound, and an acid are dissolved in a solvent to a specific composition range, thereby providing water-repellency. Since the non-transfer property (the property that no transfer occurs) is developed in the film itself, it is not necessary to take measures for preventing the transfer, such as attaching a film or applying a surfactant. As a result, effects such as an increase in man-hours and facilities and an increase in environmental load do not occur.
Claims (3)
撥水膜用液組成物として、
(A)シリコンアルコキシドまたはその加水分解物:0.05〜0.20質量%(シリカ換算)
(B)フルオロアルキル基含有シラン化合物:0.001〜0.003質量%(シリカ換算)
(C)酸:(0.01〜0.30)/酸の価数mol/l
(D)水:0.5〜2.0質量%
(E)アルコール系溶媒:残部
からなる組成範囲内の液組成物を用いて形成され、膜に接触するハンドリング治具を介して撥水成分の転写が起こらないようにしたことを特徴とする不転写性撥水膜。A silicon alkoxide or a hydrolyzate thereof, a fluoroalkyl group-containing silane compound, and a liquid composition for a water-repellent film obtained by dissolving an acid in a solvent are applied to the substrate surface, and the water-repellent film is formed by drying.
As a liquid composition for a water-repellent film,
(A) Silicon alkoxide or hydrolyzate thereof: 0.05 to 0.20% by mass (in terms of silica)
(B) Fluoroalkyl group-containing silane compound: 0.001 to 0.003% by mass (in terms of silica)
(C) Acid: (0.01 to 0.30) / valency of acid mol / l
(D) Water: 0.5 to 2.0 mass%
(E) Alcohol-based solvent: formed using a liquid composition within the composition range consisting of the remainder, and preventing transfer of the water-repellent component via a handling jig that comes into contact with the film. Transferable water repellent film.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002378153A JP2004204191A (en) | 2002-12-26 | 2002-12-26 | Non-transferring water repellent film |
EP03029340A EP1433763A1 (en) | 2002-12-26 | 2003-12-19 | Transference-less water-repellent film |
US10/743,705 US20040247898A1 (en) | 2002-12-26 | 2003-12-24 | Transference-less water-repellent film |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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JP2002378153A JP2004204191A (en) | 2002-12-26 | 2002-12-26 | Non-transferring water repellent film |
Publications (1)
Publication Number | Publication Date |
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JP2004204191A true JP2004204191A (en) | 2004-07-22 |
Family
ID=32463599
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP2002378153A Withdrawn JP2004204191A (en) | 2002-12-26 | 2002-12-26 | Non-transferring water repellent film |
Country Status (3)
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US (1) | US20040247898A1 (en) |
EP (1) | EP1433763A1 (en) |
JP (1) | JP2004204191A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US9055753B2 (en) | 2005-07-29 | 2015-06-16 | Kao Corporation | Container-packed black coffee beverage |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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US8475731B2 (en) * | 2007-09-21 | 2013-07-02 | Charm Sciences, Inc. | Lateral flow assay reader with transparent barrier in insert |
KR100915774B1 (en) * | 2009-03-09 | 2009-09-04 | (주)경동기술공사 | Waterproof agent for a facing surface containing polymethylsiloxane solution and a method of waterproof at a facing surface using the same |
US9435779B2 (en) * | 2014-05-05 | 2016-09-06 | Uop Llc | Method for quantitation of acid sites in acidic ionic liquids using silane and borane compounds |
US9435688B2 (en) * | 2014-05-05 | 2016-09-06 | Uop Llc | Method for quantitation of acid sites in acidic catalysts using silane and borane compounds |
Family Cites Families (2)
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CA2333758A1 (en) * | 1998-06-04 | 1999-12-09 | Nippon Sheet Glass Co., Ltd. | Process for producing article coated with water-repellent film, article coated with water-repellent film, and liquid composition for water-repellent film coating |
EP1136539A4 (en) * | 1999-08-02 | 2002-10-09 | Nippon Sheet Glass Co Ltd | Article coated with water-repellent film, liquid composition for coating with water-repellent film, and process for producing article coated with water-repellent film |
-
2002
- 2002-12-26 JP JP2002378153A patent/JP2004204191A/en not_active Withdrawn
-
2003
- 2003-12-19 EP EP03029340A patent/EP1433763A1/en not_active Withdrawn
- 2003-12-24 US US10/743,705 patent/US20040247898A1/en not_active Abandoned
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US9055753B2 (en) | 2005-07-29 | 2015-06-16 | Kao Corporation | Container-packed black coffee beverage |
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US20040247898A1 (en) | 2004-12-09 |
EP1433763A8 (en) | 2004-10-13 |
EP1433763A1 (en) | 2004-06-30 |
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